Búsqueda Imágenes Maps Play YouTube Noticias Gmail Drive Más »
Iniciar sesión
Usuarios de lectores de pantalla: deben hacer clic en este enlace para utilizar el modo de accesibilidad. Este modo tiene las mismas funciones esenciales pero funciona mejor con el lector.

Patentes

  1. Búsqueda avanzada de patentes
Número de publicaciónUS4954371 A
Tipo de publicaciónConcesión
Número de solicitudUS 07/070,085
Fecha de publicación4 Sep 1990
Fecha de presentación7 Jul 1987
Fecha de prioridad23 Jun 1986
TarifaPagadas
Número de publicación070085, 07070085, US 4954371 A, US 4954371A, US-A-4954371, US4954371 A, US4954371A
InventoresAngelo Yializis
Cesionario originalSpectrum Control, Inc.
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos: USPTO, Cesión de USPTO, Espacenet
Flash evaporation of monomer fluids
US 4954371 A
Resumen
A method for continuously supplying a uniform vapor of a polymerizable and/or cross-linkable material. A continuous liquid flow of said material is supplied at a temperature below both the decomposition temperature and the polymerization temperature of said material and atomized into a continuous flow of liquid droplets having a particle size from about 1 to about 50 microns. The droplets are continuously vaporized upon contact with a heated surface which is maintained at a temperature at or above the boiling point for said material, but below the temperature at which said droplets would undergo pyrolysis before vaporizing. The vapor may be deposited onto a substrate and subsequently polymerized or cross-linked.
Imágenes(3)
Previous page
Next page
Reclamaciones(23)
What is claimed is:
1. A method for continuously supplying a uniform vapor of a polymerizable material, said method comprising:
supplying a continuous liquid flow of said material at a temperature below both the decomposition temperature and the polymerization temperature of said material;
continuously atomizing the liquid flow into a continuous flow of liquid droplets; and
continuously vaporizing said liquid droplets by causing said droplets to contact a heated surface which is maintained at a temperature at or above the boiling point for said material, but below the temperature at which said droplets would undergo pyrolysis before vaporizing.
2. A method for depositing onto a substrate a layer of polymerizable material, said material being characterized by the fact that it is chemically unstable at or below its boiling point, said method comprising:
vaporizing said material by continuously placing droplets of said material into contact with a heated surface which is maintained at a temperature at or above the boiling point for said material, but below the temperature at which said droplets would undergo pyrolysis before vaporizing;
maintaining at least a portion of said substrate at a temperature which is below the boiling point of said material and in a region which is at a lower pressure than said vaporized material, to provide a positive flow of vaporized material toward said substrate; and
directing the flow of vaporized material onto said substrate.
3. The method of claim 2 wherein the substrate is maintained in a region which is at a pressure below about 10-1 Torr
4. The method of claim 2 wherein the material is polymerizable and cross-linkable and also comprising the step of polymerizing and cross-linking the material on said substrate.
5. The method of claim 4 wherein the material is polymerized and cross-linked throughout its thickness by use of electron beam curing.
6. A method for depositing a layer of a polymerizable material on a substrate comprising:
supplying a continuous liquid flow of said material at a temperature below both the decomposition and the polymerization temperature of said material;
continuously atomizing said liquid flow into a continuous flow of liquid droplets;
continuously vaporizing said liquid droplets by causing said droplets to contact a heated surface which is maintained at a temperature at or above the boiling point for said material but below the temperature at which said droplets would undergo pyrolysis before vaporizing;
maintaining at least a portion of said substrate at a temperature which is below the boiling point of said material and in a region which is at a lower pressure than said vaporized material, to provide a positive flow of vaporized material toward said substrate; and
directing the flow of vaporized material onto said substrate.
7. The method of claim 6 wherein the substrate is maintained in a region which is at a pressure below about 10-1 Torr.
8. The method of claim 6 wherein the material is polymerizable and cross-linkable and also comprising the step of polymerizing or cross-linking the material on said substrate.
9. The method of claim 8 wherein the material is polymerized and/or cross-linked throughout its thickness by use of electron beam curing.
10. A method for continuously supplying a uniform vapor of a polymerizable material, said method comprising:
providing a liquid supply of said material, at a temperature below both the decomposition temperature and the polymerization temperature of said material, to a drop just contacting a flat face of a disk;
rotating the disk so that a fluid film is pulled on the face free from the drop and a continuous flow of liquid droplets is thrown from the periphery of the disk; and
continuously vaporizing said liquid droplets by causing said droplets to contact a heated surface which is maintained at a temperature at or above the boiling point for said material, but below the temperature at which said droplets would undergo pyrolysis before vaporizing.
11. A method according to claim 10 also comprising the steps of:
maintaining at least a portion of a substrate at a temperature which is below the boiling point of said material and in a region which is at a lower pressure than said vaporized material, to provide a positive flow of vaporized material toward said substrate; and
directing the flow vaporized material onto said substrate.
12. A method according to claim 11 wherein the substrate is maintained in a region which is at a pressure below about 10-1 Torr.
13. A method according to claim 11 wherein the material is polymerizable and cross-linkable and also comprising the step of polymerizing and cross-linking the material on said substrate.
14. A method according to claim 13 wherein the material is polymerized and cross-linked throughout its thickness by use of radiation.
15. A method according to claim 14 wherein the source of radiation is an electron beam gun.
16. A method for continuously supplying a uniform vapor of a polymerizable material, said method comprising:
providing a liquid supply of said material, at a temperature below both the decomposition temperature and the polymerization temperature of said material, to an end surface at a tip of an ultrasonic vibration device;
ultrasonically vibrating said device so that the material supplied to the end surface coats the end surface and is dispersed in droplets from the periphery of the end surface; and
continuously vaporizing said liquid droplets by causing said droplets to contact a heated surface which is maintained at a temperature at or above the boiling point for said material, but below the temperature at which said droplets would undergo pyrolysis before vaporizing.
17. A method according to claim 16 wherein the ultrasonic vibration device is fixedly mounted at a nodal point.
18. A method according to claim 17 wherein the end surface is positioned with respect to the mounting of the device so as to be at the maximum amplitude of motion for the device while it is vibrating.
19. A method according to claim 16 also comprising the steps of:
maintaining at least a portion of a substrate at a temperature which is below the boiling point of said material and in a region which is at a lower pressure then said vaporized material, to provide a positive flow of vaporized material toward said substrate; and
directing the flow of vaporized material onto said substrate.
20. A method according to claim 19 wherein the substrate is maintained in a region which is at a pressure below about 10-1 Torr.
21. A method according to claim 19 wherein the material is polymerizable and cross-linkable and also comprising the step of polymerizing and cross-linking the material on said substrate.
22. A method according to claim 21 wherein the material is polymerized and cross-linked throughout its thickness by use of radiation.
23. A method according to claim 22 wherein the source of radiation is an electron beam gun.
Descripción

This application is a continuation of Ser. No. 877,175, filed June 23, 1986, now abandoned.

FIELD OF THE INVENTION

The present invention relates to a method for depositing a liquid film on a substrate and, more particularly, to a method for depositing a monomeric film on a substrate. Such a film may be polymerized or cross-linked to form a polymeric layer on said substrate.

CROSS-REFERENCES

This invention is related to the following copending, commonly assigned, U.S. patent applications and patents: Ser. No. 620,647, filed June 14, 1984, now abandoned, entitled "Miniaturized Monolithic Multi-layer Capacitor and Apparatus and Method for Making"; U.S. Pat. No. 4,499,520, issued Feb. 12, 1985, entitled "Capacitor with Dielectric Comprising Poly-Functional Acrylate Polymer and Method of Making"; U.S. Pat. No. 4,490,774, issued Dec. 25, 1984, entitled "Capacitors Containing Polyfunctional Acrylate Polymers as Dielectrics"; U.S. Pat. No. 4,533,710, issued Aug. 6, 1985, entitled "1,2-Alkanediol Diacrylate Monomers and Polymers Thereof Useful as Capacitor Dielectrics"; U.S. Pat. No. 4,513,349, issued Apr. 23, 1985, entitled "Acrylate-Containing Mixed Ester Monomers and Polymers Thereof Useful as Capacitor Dielectrics"; U.S. Pat. No. 4,515,931, issued May 7, 1985, entitled "Polyfunctional Acrylate Monomers and Polymers Thereof Useful as Capacitor Dielectrics"; U.S. Pat. No. 4,586,111, issued Apr. 29, 1986, entitled "Capacitor with Dielectric Comprising a Polymer of Polyacrylate Polyether Pre-Polymer"; Ser. No. 668,918, filed Nov. 6, 1984, entitled, "Atomizing Device for Evaporation" now abandoned; and Ser. No. 692,746, filed Jan. 18, 1985, entitled "Monomer Atomizer for Evaporator", now abandoned; all of which are hereby incorporated by reference.

BACKGROUND AND OBJECTS OF THE INVENTION

Various industries require the ability to place thin coatings of polymeric materials onto selected substrates. One such industry is the electronics industry, especially the portion thereof which is concerned with the manufacture of polymer monolithic capacitors. Other industries which rely on the production of thin polymeric coatings on various substrates include magnetic tape manufacturers and producers of packaging films.

Capacitors are used in a wide variety of electrical circuits, for example, in relatively high voltage AC power systems (such as the common 110-volt systems) and in relatively low voltage (e.g., under 50 volts) DC systems frequently encountered in printed circuits and the like. Important factors which must be considered in the manufacture of such capacitors are volumetric efficiency, temperature of operation, dissipation factor, especially in AC systems, and behavior upon failure.

The development of electronic devices and circuits of reduced size has led to a need for significantly smaller capacitors having increased volumetric efficiency, or capacitance per unit volume. The polymer monolithic capacitor has been used for such applications.

A monolithic capacitor is one in which the layers of electrodes and dielectric are bonded together in a unitary structure as opposed, for example, to a metallized film capacitor in which self-supporting films are rolled or wound into the capacitor form. A miniaturized capacitor is one of very small dimensions, so as to be suitable for microcircuitry. Small overall size could denote low capacitance of little practical value, except that the thickness of the intervening dielectric layer inversely affects the capacitance between adjacent electrodes, and the number of electrode pairs and dielectric constant of the dielectric directly affects capacitance. Therefore, as a matter of basic capacitor theory, a capacitor having very thin dielectric layers, and many pairs of electrodes or a given capacitor with a dielectric having a high dielectric constant could have substantial capacitance despite being of miniature size with the active area of the electrodes being quite small.

One such type of polymer monolithic multi-layer capacitor is described in application Ser. No. 620,647, now abandoned, cross-referenced herein. That capacitor has a capacitively active section, and two electrode joining sections, each separated from the active section by a sloping section. The capacitor includes a first and second set of electrode layers interleaved with one another, each layer of each set having an active area extending through and contributing to the capacitively active section of the capacitor in a stacked and spaced apart relationship with the active areas of all of the other layers. The electrode layers are joined at the margin in stacked electrically contacting relationship and each layer has a sloped portion between its active area and its margin which contributes to a sloped section of the capacitor. A dielectric coating is in contact with and between each adjacent electrode pair. The dielectric coating has a substantially uniform thickness in the capacitively active section and tapers to zero thickness through the sloping section.

The volumetric efficiency of a capacitor, including the monolithic multi-layer capacitor described above, is normally measured in terms of capacitance per unit volume. Generally, high efficiency is desirable, with values of at least about one-tenth (0.1) microfarad per cubic millimeter for a 50 VDC rated unit being preferred.

As noted above, the volumetric efficiency of the capacitor may be increased by reducing the thickness of the dielectric layer and/or by increasing the number of electrode pairs, both of which may have limits depending upon the capacitor type and its end use.

From the foregoing, it is evident that in order to achieve the results which are desired in accordance with the aforementioned application Ser. No. 620,647, a method for depositing a thin uniform monomeric layer on the desired substrate is absolutely essential. Heretofore, it has been known generally in the art that monomeric layers may be deposited upon substrates. For example, U.S. Pat. No. 3,547,683 and the British counterpart thereof, No. 1,168,641 deal with the vapor deposition of a polymerizable or cross-linkable material which has a vapor pressure under standard temperature and pressure conditions of less than 1 Torr. It appears that the concept embodied in such patents is simply to allow a heated container of the material to vaporize the desired polymerizable or cross-linkable material Such an approach suffers from the fact that by maintaining a polymerizable or cross-linkable material at an elevated temperature for any substantial length of time gives rise to the possibility of degradation and/or polymerization of the material, within the container, both of which are undesirable.

U.S. Pat. Nos. 4,121,537 and 4,207,836 are both concerned with the vapor deposition of a layer of a compound consisting of two or more kinds of elements such as Se, Te or As through flash evaporation, as by dropping raw material, bit-by-bit, into a boat heated to a high temperature with the individual bits being vaporized within a short time. Thus, the approach of using flash evaporation is not taught in said patents to relate to monomeric materials as used in the present invention. A problem with such an approach, as taught in said patents, of course, is that as each drop is vaporized, a burst of vapor is produced, followed by an intermittent period of time during which no vapor is present. Under such conditions, it is difficult to achieve a uniform layer of material on the desired substrate. The foregoing is especially true if the source of the vapor and the substrate are moving in relation to each other.

U.S. Pat. No. 4,153,925 is concerned with the use of electron bombardment or ultraviolet radiation of an organic monomer to make a dielectric layer, generally. However, there is no specific teaching regarding the method by which the monomer is placed on the desired substrate. Likewise, U.S. Pat. Nos. 4,277,516; 4,301,765 and 4,378,382 deal with the glow polymerization of monomers, without any specific indication of how one might achieve a desired uniform monomeric layer. It is believed that the monomers which are glow polymerized and to which those patents relate, are monomers which are typically present under standard temperature and pressure conditions as a gas and thus do not present the same problem as do monomers which are typically used as liquids.

Thus, especially in view of the process disclosed in the aforementioned application, Ser. No. 620,647, now abandoned, there exists a need for a method by which polymerizable and/or cross-linkable materials may be uniformly deposited upon a desired substrate in a controlled manner such that said materials may be subsequently cured to form a desired polymeric layer on said substrate. More generally, a need exists for a method by which materials may be quickly and uniformly deposited upon a desired substrate.

SUMMARY OF THE INVENTION

Generally, the present invention provides a method for depositing onto a substrate a layer of material, which may be a polymerizable and/or cross-linkable material, said material being characterized by the fact that it is chemically unstable at or below its boiling point, said method comprising vaporizing said material by continuously placing droplets of said material into contact with a heated surface which is maintained at a temperature at or above the boiling point for said material, but below the temperature at which said droplets would undergo pyrolysis before vaporizing; maintaining at least a portion of said substrate at a temperature which is below the boiling point of said material and in a region which is at a lower pressure than said vaporized material, to provide a positive flow of vaporized material toward said substrate; and directing the flow of vaporized material onto said substrate in a predetermined manner.

In accordance with the present invention, there is also provided a method for continuously supplying a uniform vapor of a material, which may be a polymerizable and/or cross-linkable material, said method comprising supplying a continuous liquid flow of said material at a temperature below both the decomposition temperature and the polymerization temperature of said material, continuously atomizing the liquid flow into a continuous flow of airborne liquid droplets having a particle size from about 1 to about 50 microns, and continuously vaporizing said liquid droplets by causing said droplets to contact a heated surface which is maintained at a temperature at or above the boiling point for said material, but below the temperature at which said droplets would undergo pyrolysis before vaporizing.

The present invention thus also provides a method for depositing a layer of a material, which may be a polymerizable and/or cross-linkable material, on a substrate comprising supplying a continuous liquid flow of said material at a temperature below both the decomposition and the polymerization temperature, if any, of said material; continuously atomizing said liquid flow into a continuous flow of liquid droplets having a particle size from about 1 to about 50 microns; continuously vaporizing said liquid droplets by causing said droplets to contact a heated surface which is maintained at a temperature at or above the boiling point for said material but below the temperature at which said droplets would undergo pyrolysis before vaporizing; maintaining at least a portion of said substrate at a temperature which is below the boiling point of said material and in a region which is at a lower pressure than said vaporized material, to provide a positive flow of vaporized material toward said substrate; and directing the flow of vaporized material onto said substrate in a predetermined manner.

From the foregoing, it should also be apparent that when the material is polymerizable and/or cross-linkable, by employing the additional step of polymerizing or cross-linking the material on said substrate, a method is also provided for depositing a polymeric coating on at least a portion of the desired substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic perspective of an apparatus useful in the practice of the method of the present invention;

FIG. 2 is an enlarged fragmentary section of a portion of the apparatus shown in FIG. 2 illustrating the operating phenomenon created;

FIG. 3 is a top view, with a portion sectioned, of the structure shown in FIG. 2;

FIG. 4 is similar to FIG. 3 but illustrates the droplet dispersion resulting from operation of the apparatus;

FIG. 5 is a schematic partially sectioned apparatus embodying an atomizer useful in performing the process in accordance with the invention; and

FIG. 6 is a schematic of an apparatus used to manufacture polymer monolithic capacitors, employing the method of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As discussed, the present invention provides a method for depositing a uniform film of a polymerizable and/or cross-linkable material onto a substrate. The polymerizable and/or cross-linkable material may be referred to hereinafter as a monomer or monomeric material. However, as will be detailed below, the material may itself be polymeric in nature.

Thus, the monomers which are useful in the present invention include all such materials disclosed in the cross-referenced applications discussed above, which are hereby specifically incorporated by reference.

In addition, other monomeric materials which are useful in the practice of the present invention include those discussed in U.S. Pat. No. 3,547,683, including, but not limited to, low molecular weight addition-type polymers, natural oils, silicone, condensation polymers, and other monomers and materials containing unsaturation which are capable of undergoing polymerization or cross-linking.

From the viewpoint of operability in the present process, any monomer employed herein should either be a liquid at room temperature or should be capable of being converted to a liquid at an elevated temperature, without undergoing any significant decomposition or polymerization. Furthermore, the monomeric materials should have a vapor pressure at standard temperature and pressure, of less than about 1 Torr and preferably less than about 10-3 Torr. It is also contemplated that monomers useful in the present invention include those monomers which, although not themselves a liquid at room temperature are capable of being dissolved in other suitable liquids to form an azeotropic solution.

The particularly preferred monomeric materials for use in the present invention are the polyacrylate polyether prepolymers disclosed in the cross-referenced U.S. Pat. No. 4,586,111, issued Apr. 29, 1986.

The monomers used in the present invention are generally characterized by the fact that they are chemically unstable at temperatures at or even below their boiling point. The term "chemically unstable" is used herein to refer to any type of chemical instability, including, but not limited to, oxidation or other chemical degradation of the monomer as well as the formation of polymers or oligomers.

As indicated above, the first step in the method of the present invention involves continuously supplying droplets of the monomer. Such droplets may be produced by continuously supplying a stream of the liquid monomer and continuously atomizing said monomer into a continuous flow of droplets which preferably are uniform liquid droplets having a particle size from about 1 to about 50 microns. Typically, the particle size of the liquid droplets will be from about 1 to about 20 microns and most typically will be centered around particles having a particle size from about 5 to about 10 microns.

Although, in general, the atomized droplets employed in the present process will fall within the size range of about 1 to about 50 microns, it is theoretically best to use the smallest particle size possible. Thus, particles of less than 1 micron in size may be advantageously employed in the present invention. However, from a practical viewpoint, it is not usually possible to atomize the monomers into such a fine particle size, so other considerations must be used to determine the largest particle size which will be acceptable.

It is, of course, to be appreciated that when discussing the largest particle size employed in any given embodiment of the present invention, the actual droplets employed will have a particle size distribution range peaking at some level significantly below the maximum particle size. Thus, for example, in a typical embodiment of the present invention the particle size employed may range from about 1 to about 20 microns, with the distribution peak occurring at about 10 microns. As used herein, it is to be appreciated that the "particle size" of a particle is meant to refer to the diameter of that particle.

It should be understood that a principal goal of the present invention is to achieve vaporization of the monomer particles from the heated surface in such a manner that no fluid accumulates on said substrate. Thus, to achieve a continuous flow of monomer vapor by vaporizing monomer droplets from the heated surface, the size of those monomer droplets typically needs to be such that the vaporization of the monomer deposited from each droplet will occur in less than about 50 milliseconds, more typically within less than about 20 milliseconds, and most typically within less than about 10 milliseconds. Ideally, it would be preferred for the vaporization of the monomer to occur in less than 1 millisecond. However, practical limitations again usually dictate that the vaporization occur in the range from about 10 to about 20 milliseconds. The actual length of time needed for vaporization is, of course, dependent upon many considerations, besides the size of the monomer droplet. Such considerations include the nature of the monomer, such as its vapor pressure under standard temperature and pressure conditions, the degree of vacuum under which the heated surface is placed, and the temperature to which the surface is heated.

The exact mechanism for atomizing said liquid monomer, in general, is not critical and any suitable method may be employed. However, for many applications it is critical that the method of atomizing said liquid monomer be precise in that substantially all of the particles fall within the desired size range and that the particles are supplied in a continuous flow which is thus not intermittent in nature. The need for the continuous flow is evident when considering the fact that the typical ultimate use may be the deposition of a uniform polymer layer as, for example, a dielectric coating in a monolithic capacitor structure.

One suitable method for atomizing the liquid monomer is disclosed in the cross-referenced application Ser. No. 668,918 and another such method is disclosed in Ser. No. 692,746, filed Jan. 18, 1985, entitled "Monomer Atomizer for Evaporation".

Employing the apparatus taught in either of the two aforementioned applications in the manner described therein will result in the generation of monomer particles of the desired size range, in a continuously flowing, uniform stream. Any other device may be employed to atomize the liquid monomer, so long as it results in the generation of the desired size of particles in a uniform, continuous flow.

With respect to the step of vaporizing the liquid droplets, again, any suitable heated surface may be employed. The temperature of the heated surface should be such that vaporization occurs instantaneously upon contact with the surface by the monomer droplets. However, the temperature should also not be so high as to cause pyrolysis of the material, that is to cause oxidation or other degradation of the monomer structure itself.

With respect to the physical form of the heated surface, any desirable shape may be employed. Various structures are shown in the cross-referenced applications. It is usually desirable for the heated surface to be contained in or to actually form a vaporization chamber in which the liquid droplets may be vaporized. Such a chamber may also define a means for directing the flow of monomer vapor onto a substrate. In such an embodiment, the chamber may terminate in the form of a flow directing means, or nozzle, such that the liquid monomer droplets upon being vaporized create an internal pressure within the chamber causing the monomer vapor to be expelled out the nozzle or other flow directing means in the direction of the substrate.

In the manufacture of monolithic capacitors, the preferred substrate is a copper sheet. As may be appreciated, in the manufacture of monolithic capacitors, the copper sheet may itself be coated with layers of polymeric material, alternating with layers of conducting material, such as aluminum about 200 to 500 angstroms thick. Thus, a typical substrate would be a copper sheet on which alternating layers of polymeric material formed through the method of the present invention and alternating conducting layers of aluminum are present.

The substrate itself should be located in a region which is maintained at a lower pressure than the pressure generated through the vaporization of the monomer droplets. With respect to the pressure employed as in the manufacture of monolithic capacitors, the pressure in the deposition zone is usually below 10 Torr, preferably below 10-1 Torr and advantageously 10-4 Torr, or even less.

The layer of film of monomeric material deposited on the substrate may be any suitable depth. However, the depth of the deposited film should usually be such that the subsequent means of polymerization or cross-linking will be effective in curing the monomeric material throughout substantially its entire depth.

With respect to the step of polymerizing the deposited film, any suitable methods may be employed. Thus, thermal, electron beam, or ultraviolet radiation curing may be employed, depending upon the nature of the monomer. A particularly suitable method for curing employs the use of a beam of accelerated electrons whose energy is generally up to about 20 kev, as are available from conventional electron accelerators. The energy of the irradiation and the length of time for which the monomeric film is exposed to the radiation should be such as to polymerize or cross-link the material throughout its thickness The present invention, in its preferred embodiments, may be further appreciated by reference to the drawings and the following description.

Two different apparatus have been developed for flash vaporizing a liquid according to the present invention. These apparatus will now be described in detail. It is to be understood, however, that these apparatus are not the only apparatus which can be used in practicing the present invention. Any apparatus capable of continuously atomizing a liquid to the appropriate particle size and continuously vaporizing the liquid particles in contact with a heated surface could be used to advantage in the present invention.

Turning to FIG. 1, there is shown a first embodiment of an apparatus 10 for vaporizing a liquid, such as a monomeric resin, supplied in a reservoir 11 and depositing by condensing the resulting vapor on a substrate 12 arranged to move past the apparatus 10. It will be understood that both the apparatus 10 and the substrate 11 are maintained in a low vacuum environment. The intent of the vapor deposition is to deposit a uniform, very thin--one micron or less--coating of the liquid material on the substrate 12.

The apparatus includes a vaporization chamber 13 formed with a nozzle opening 14 for emitting the vaporized material in close proximity to the substrate 12. The chamber 13 encloses a spinning disk 15 driven by a motor 15 which throws by centrifugal force atomized droplets of fluid against a band heater 17 defining a heating surface 18 surrounding the disk 15. The tiny droplets are flash upon contact with the heated surface 18, thereby developing both vapor and vapor pressure to expel the gaseous material through the nozzle opening 14 for condensation on the substrate 12. When the fluid is a monomeric liquid, the flash vaporization preserves the chemical structure, and the condensed monomer film on the substrate can be later cured, if desired, by any suitable technique such as applying ultraviolet or electron beam radiation.

In accordance with the invention, the atomizing device includes, in addition to the driven disk 15, a capillary tube 20 mounted on the reservoir 11 for delivering fluid at right angles to the flat circular face 21 of the disk 15, and the end of the tube 20 is spaced from the face 21 so that a liquid drop formed at the tube end is just contacted by the face. With the proper spacing, disk face speed and drop size, the face rotates the drop as shown in FIG. 2 while pulling a fluid film on the face 21 free from the drop, which fluid film is continuously replenished from the tube 20, and the film is thrown centrifugally in atomized droplets having a particle size from about 1 to about 20 microns, from the periphery of the disk onto the heated vaporizing surface 18. The droplets will be thrown from the disk surface 21 along the path lines 22 illustrated in FIG. 4.

If the tube 20 is initially positioned near the center of the spinning disk 15 and then moved peripherally outward so as to gradually increase the speed of the surface contacting the drop, the condition described above and illustrated in FIG. 2 will be reached. Representative relationships found suitable for a monomeric liquid resin included a 20 mil capillary tube feeding liquid to a disk 1" in diameter driven in the 3,000 to 5,000 rpm range. The formed drop, depending upon the liquid's viscosity and surface tension, contacted the disk with the tube end spaced about 37 mils from the disk. The disk was formed of clean glass. The drop rolling and film forming phenomenon was achieved with the spacing 23 (see FIG. 3) of the drop from the disk center being about 3/8". Droplets are produced and discharged along the paths 22.

While the disk surface 21 has been illustrated as horizontal with the tube at a vertical right angle, the surface 21 can be disposed vertically and the tube horizontal so long as the tube is positioned so that the drop contacts the upwardly driven half of the disk surface. So disposed, the viscosity pull of the disk on the liquid counteracts the gravity pull.

The arrangement described produces a continuous rate of very low volume droplets well suited for subsequent flash vaporization and deposition of a very thin coating layer. The vapor delivery rate can be increased, if desired, by pressurizing the reservoir 11. Liquids of varying viscosity would produce initial droplets of varying size depending upon the size of the capillary tube, but the disk and tube relative spacing could obviously be readily varied to accommodate varying drop sizes.

FIG. 5 is a schematic partially sectioned apparatus embodying a second, and presently preferred, embodiment of an atomizer useful in performing the process in accordance with the invention.

Turning to FIG. 5, there is shown another apparatus 110 for vaporizing a monomeric liquid supplied through a line 111 and valve 112, and vacuum depositing the vapor onto a surface 113 carried by a rotating drum 114. The liquid is atomized by a structure 115 embodying the invention, vaporized in a vaporization chamber 116 heated by heaters 117, and deposited through nozzle structure 118 onto the drum surface 113. The nozzle structure 118 controls the vapor deposition in part by confining vapor flow with inert gas, supplied through a line 121 and valve 122. The apparatus 110 is mounted within a vacuum chamber 123.

In accordance with this second and preferred embodiment, the structure 115 is essentially integrally formed with a tip portion 131 at one end extending, and delivering liquid, into the vaporization chamber 116 and having an ultrasonic vibration device 132 coupled at the opposite end. The structure 115 is supported by a collar 134 that closes the chamber opening through which the tip portion 131 extends and which is fixed to the tip portion at approximately its nodal point. The tip portion 131 has a necked-down tip 135 ending in a surface 136 to Which the liquid is directed through a capillary passage 137 in the tip portion 131 that is connected to the liquid feed line 11 by a compression coupling 138. The device 132, preferably a piezoelectric crystal transducer, is energized by an electronic power supply 139 through a line 141. Ultrasonic vibration of the tip 135 and its surface 136 causes the liquid to flow from the passage 137, coat the surface 136 and be dispersed in fine droplets through a widespread pattern in the chamber 116. The pattern seen is in the form of a shallow cone when a substantially flat surface like the surface 136 is utilized. Upon striking the hot chamber walls, temperatures of 350° to 400° F. being typical, the liquid is vaporized, creating gaseous pressure driving the vapor through the nozzle structure 118 so as to be deposited on the surface 113.

The lengths of the coupling 143 and tip portion 131 correspond to one-half wavelength of the vibration, and the device 132 is operated at their fundamental frequency mode with maximum amplitude of motion at the surface 136 and minimum movement, or node positions, at the attachment points of the coupling 143 and tip portion 131. To protect the vibration device 132 from heat, the structure 115 includes a cooling coupling 143 interposed between and rigidly connected to the tip portion 131 and the vibration device 132. Cooling water is directed through a passage in the coupling 143 using lines 144. The coupling 143 and the cooling water absorb and remove heat conducted from the vaporization chamber 116 along the tip portion 131 so that extreme temperatures cannot adversely affect the vibrating device 132. To minimize vibration absorption, the lines 138, 144 and the connection with the collar 134 are located at or near the vibration node positions. The structure 115 is left supported cantilever fashion by the collar 134 so that the device 132 can vibrate undampened.

It has been found that a material like titanium alloy 6AL4V is suitable for the tip portion 131. The diameter of the passage 137 is dependent upon the flow rate of the liquid being conveyed through the line 111, and diameters of 20 mils to 1/8" have been found suitable.

The basic structure represented by the tip portion 131, vibration device 132 and electronics 139 can be found in standard laboratory equipment such as ultrasonic emulsifying devices and this utilization of relatively standard components makes the atomizer structure economical to manufacture and maintain.

Capacitors made using the method of the present invention may be formed of materials and in configurations known in the art. The conductive materials are typically aluminum, zinc, alloys of these metals and bi-layers involving at least aluminum or zinc and another metal, with aluminum being preferred. Aluminum and zinc are unique because of their contribution to the self healing properties of a capacitor. For example, one embodiment of the present invention provides a capacitor which includes a first electrode which may be, for example, an aluminum layer, a dielectric coating of a polymer formed by deposition of a monomeric material in solution, on the surface of the first electrode by the method of the present invention, followed by polymerization and a second electrode which is a second thin metallized layer preferably of aluminum deposited on the dielectric film Suitable leads are attached to the first and second electrodes.

The present invention likewise is useful in the manufacture of polymer monolithic multi-layer capacitors such as those described and claimed in application Ser. No. 620,647. Capacitors of this type may be produced by depositing alternating electrode and dielectric layers so as to provide alternate electrode layers with portions projecting from the stack and contacting each other in electrically connected relation as more fully described in that application. The dielectric coating comprises a polymer which is formed by using the method of the present invention to deposit a layer of a monomeric material on the electrode and subsequent polymerization of the monomeric material. The use of electron beam polymerization is particularly preferred because it provides rapid polymerization of the pre-polymer without the need for additional curing agents, and thus leads to economical production of very thin coatings.

The method of the present invention wherein the layer of monomeric material is deposited on a substrate and subsequently polymerized or cross-linked may thus be employed in the manufacture of polymer monolithic capacitors using an apparatus arranged as shown in FIG. 6 which includes apparatus arranged within and around a chamber 230 which is either a vacuum chamber or a housing divided into vacuum portions. Within a vacuum environment is a carrier 231, a dielectric deposit system 232, a monomer curing system 233, and an electrode material deposit system 234. A substantial vacuum is required down to the order of 1×10-4 Torr.

The carrier 231 is a water cooled drum 235 driven by a motor 236 and whose outer cylindrical surface 237 defines a rapidly moving continuous surface passing .through a dielectric forming zone and an electrode forming zone. The regions in which the drum surface 237 and the systems 232, 233 are located constitute the dielectric forming zone, and the region in which the drum surface 237 and the system 234 are located constitute an electrode forming zone. Drum rotation creates the machine direction 226, which is the direction the surface passes through the dielectric forming zone and the electrode forming zone.

Because of the small dimensions involved, the surface 237 should be smooth and true. The sheet of substrate 213 is firmly secured to the drum 35 and, when in place, the outer surface of the substrate defines the surface 237. The drum 235 is cooled to about 70° F. so as to facilitate condensation of the vapor deposits, and the apparatus functions at drum surface speeds of 150 to 600 feet per minute.

The electrode material deposit system 234 includes a conventional electron beam vaporization device 241 such as those used for metallizing film within a vacuum environment. The rate of vaporization is sensed by a conventional quartz monitoring device 242 providing feedback for controlling the rate at which aluminum is vaporized by the device 241.

The alternate pattern of metal vapor deposition is obtained by shifting the mask 243 axially of the drum 235 upon each drum revolution. A mask motor 247 makes the shifting movement through a simple mechanical connection 248. A controller 250 is connected to the drum motor 236 for sensing drum revolution, and the controller 250 supplies the appropriate shifting signal to the mask shifting motor 247. It is desirable to keep the mask 243 close to the surface onto which the metal vapor is being deposited, and this closeness is maintained by a mask retraction motor 251 which steps the mask away from the surface 237 upon each drum revolution, as signalled by the controller 250, through a distance approximating the thickness of the electrode layer being deposited.

As it is convenient to energize the device 241 and bring it into stable operating condition before beginning to make capacitors, a removable shutter 252 is interposed between the device 241 and the mast 243 for closing off the passage of vapor until the shutter 252 is withdrawn.

As a feature of the invention, the dielectric deposit system 232 flash vaporizes the dielectric in monomer form as discussed above in conjunction with FIGS. 1 through 5.

The condensed liquid monomer is radiation cured by the second system 233 in the dielectric forming zone which includes a radiation source, preferably a gas discharge electron beam gun.

The overall operation of the apparatus of FIG. 6 can now be readily understood. Electrode layers are deposited, coated with dielectric and the dielectric cured, before the surface on which the electrode layers are deposited passes again for successive electrode layers and dielectric coatings. Desired thicknesses of the electrode layers and dielectric coatings are determined by matching the rate of vapor deposition with the surface speed of the drum 235.

The above description has paid particular attention to application of the method of the present invention in making polymer monolithic multi-layer capacitors. However, the method of the present invention should not be understood as being limited to such an application or even limited to depositing a monomeric film on a substrate for subsequent polymerization and/or cross-linking. The method of the present invention can be used to advantage in any application requiring a controlled supply of vaporized material. For example, if the material to be evaporated is a mixture of components having different vapor pressure, flash vaporization provides a supply of vapor wherein the components are present in the same ratios as in the mixture. This would not be true of a supply of vapor created by bulk evaporation of the mixture. Thus, flash vaporization is particularly beneficial in any application requiring a controlled supply of a vaporized mixture, such as chemical vapor deposition.

Citas de patentes
Patente citada Fecha de presentación Fecha de publicación Solicitante Título
US30285 *9 Oct 1860 Fruit-drier
US1318774 *8 Abr 191814 Oct 1919 Method of and means fob intimate mixing of fltjids
US1766699 *28 Sep 192724 Jun 1930Ig Farbenindustrie AgApparatus for continuous distillation of difficultly-distillable liquids
US2048888 *8 Sep 193428 Jul 1936Ott Frank HCooling device
US2192140 *31 Jul 193727 Feb 1940Chicago Television & Res Lab IDevice for transferring liquids in vacuum
US2229313 *21 Abr 193921 Ene 1941Snyder Charles RCarburetor
US2258445 *6 Feb 19407 Oct 1941Du PontApparatus for vaporization
US2265762 *9 Abr 19409 Dic 1941Shell DevSeparation of phases with the aid of sonic waves
US2313976 *18 Ene 194116 Mar 1943Claude R WickardApparatus for dispersing insecticides
US2614524 *5 Jun 194821 Oct 1952Rca CorpCapacitor manufacturing evaporation apparatus
US2695871 *25 Sep 195130 Nov 1954Abbott LabRotary molecular vacuum still
US2734478 *29 Dic 195114 Feb 1956 Copper
US2949900 *2 Jun 195823 Ago 1960Albert G BodineSonic liquid sprayer
US3081201 *20 May 196012 Mar 1963Gen ElectricMethod of forming an electric capacitor
US3130066 *9 Oct 196121 Abr 1964Ransburg Electro Coating CorpElectro spray apparatus and method
US3192167 *20 Sep 196229 Jun 1965Ogawa AbikoLow pressure liquid vaporizer which is electrically heated
US3193261 *1 Dic 19606 Jul 1965Mc Graw Edison CoHumidifier
US3306829 *27 Abr 196628 Feb 1967Arthur H Thomas CompanyMagnetic stirrer in a still
US3328610 *13 Jul 196427 Jun 1967Branson InstrSonic wave generator
US3358931 *16 Jul 196519 Dic 1967Bosch Gmbh RobertPainting apparatus
US3369976 *26 May 196620 Feb 1968Foster Grant Co IncApparatus for condensing a gaseous mixture of monomer and oligomers of polymeric materials
US3400892 *2 Dic 196510 Sep 1968Battelle Development CorpResonant vibratory apparatus
US3439477 *26 Abr 196822 Abr 1969Nat Res DevApparatus for gas filtration
US3547683 *19 Jun 196715 Dic 1970British Iron Steel ResearchVacuum deposition and radiation polymerisation of polymer coatings on substrates
US3620509 *24 Ene 196916 Nov 1971Roman Vernon AGas washer
US3902857 *13 Ago 19732 Sep 1975Allied ChemThin film reactor
US3904713 *10 Oct 19729 Sep 1975Cherne Ind IncLiquid cooling apparatus
US3978174 *2 Jun 197531 Ago 1976Great Plains Industries, Inc.Evaporator cooler apparatus
US4076866 *30 Mar 197528 Feb 1978Massachusetts Institute Of TechnologyMethod of growing films by flash vaporization
US4085893 *3 Sep 197625 Abr 1978Durley Iii Benton AUltrasonic humidifiers, atomizers and the like
US4121537 *21 Mar 197724 Oct 1978Hitachi, Ltd.Apparatus for vacuum deposition
US4153925 *6 Feb 19788 May 1979Thomson-CsfDielectric formed by a thin-layer polymer, a process for producing said layer and electrical capacitors comprising this dielectric
US4207836 *22 Jun 197817 Jun 1980Hitachi, Ltd.Vacuum vapor-deposition apparatus
US4261798 *17 Dic 197914 Abr 1981Bp Chemicals LimitedFlash vaporization in vacuo, condensation in presence of polymerization inhibitors
US4264539 *12 Dic 197928 Abr 1981Samuel Ray DickensonLiquid fuel vaporizer
US4267976 *10 Mar 197819 May 1981Chatwin Francis RApparatus for vaporizing and atomizing liquids
US4277025 *21 Jun 19797 Jul 1981Plessey Handel Und Investments AgVibratory atomizer
US4277516 *28 Dic 19797 Jul 1981Siemens AktiengesellschaftPlurality of glow polymerization layers and intervening metal layers; for electrical capacitors
US4301765 *27 Ago 198024 Nov 1981Siemens AktiengesellschaftApparatus for generating layers on a carrier foil
US4311275 *12 Dic 197919 Ene 1982Lindkvist Allan ErikDevice for use in apparatus for thermal spraying
US4323524 *9 May 19806 Abr 1982Imperial Chemical Industries LimitedProduction of fibres
US4338876 *2 Jul 198013 Jul 1982Sir James Farmer Norton & Company LimitedApplication of liquids to textiles
US4376329 *17 Nov 198015 Mar 1983Siemens AktiengesellschaftMethod for producing an improved electrical layer capacitor
US4378382 *16 Jul 198129 Mar 1983Siemens AktiengesellschaftMethod and apparatus for producing laminated capacitors
US4387113 *2 Mar 19827 Jun 1983Siemens AktiengesellschaftMethod of producing electrical layer capacitors with glow-polymerizate layers as dielectrics
US4466571 *22 Jun 198221 Ago 1984Muehlbauer ReinhardHigh-pressure liquid injection system
US4543275 *16 Sep 198324 Sep 1985Fuji Photo Film Co., Ltd.Method of forming thin vapor deposited film of organic material
EP0036617A2 *17 Mar 198130 Sep 1981Siemens AktiengesellschaftFuel injector with further fuel atomizing
EP0147696A2 *7 Dic 198410 Jul 1985SPECTRUM CONTROL, INC. (a Pennsylvania corporation)Miniaturized monolithic multi-layer capacitor and apparatus and method for making
GB1104172A * Título no disponible
GB1168641A * Título no disponible
GB1253124A * Título no disponible
JPH09177365A * Título no disponible
JPS54136435A * Título no disponible
JPS59177365A * Título no disponible
Otras citas
Referencia
1Vol. 10 #258 (c-370) (2314) Sep. 4, 1986, JP 61-84367 (A) (ULVAC CORP) (and translation).
2 *Vol. 10 258 (c 370) (2314) Sep. 4, 1986, JP 61 84367 (A) (ULVAC CORP) (and translation).
3Vol. 9 #306 (c-317) (2029), Dec. 3, 1985, JP 60-145372 (A) (Furukawa Denki Kogyo K.K.).
4 *Vol. 9 306 (c 317) (2029), Dec. 3, 1985, JP 60 145372 (A) (Furukawa Denki Kogyo K.K.).
Citada por
Patente citante Fecha de presentación Fecha de publicación Solicitante Título
US5204314 *13 Dic 199120 Abr 1993Advanced Technology Materials, Inc.Flash vaporization of Group II beta-diketonate source material to form superconducting oxide and Group II fluorides
US5440446 *4 Oct 19938 Ago 1995Catalina Coatings, Inc.Acrylate coating material
US5536323 *25 Jul 199416 Jul 1996Advanced Technology Materials, Inc.Apparatus for flash vaporization delivery of reagents
US5545375 *3 Oct 199413 Ago 1996Becton, Dickinson And CompanyBlood collection tube assembly
US5665280 *2 Oct 19969 Sep 1997Becton Dickinson CoBlood collection tube assembly
US5681615 *27 Jul 199528 Oct 1997Battelle Memorial InstituteDissolving a salt in a monomer solution, vacuum flash evaporating the solution, condensing evaporated solution as a liquid film, and depositing the composite material on to a substrate in vacuum atomosphere
US5683771 *30 Ene 19964 Nov 1997Becton, Dickinson And CompanyBlood collection tube assembly
US5686157 *30 Ene 199611 Nov 1997Becton, Dickinson And CompanyMultilayer barrier coating of polyvinylidene chloride
US5702770 *30 Ene 199630 Dic 1997Becton, Dickinson And CompanyApplying a barrier film to interior wall of plastic substrate
US5711816 *7 Jun 199527 Ene 1998Advanced Technolgy Materials, Inc.Source reagent liquid delivery apparatus, and chemical vapor deposition system comprising same
US5716683 *30 Ene 199610 Feb 1998Becton, Dickinson And CompanyTesting plastic container comprising multilayer protective coatings containing polyepoxides undercoatings and metal oxide inorganic overcoatings; gas impervious, shelf life, chemical resistance
US5719417 *27 Nov 199617 Feb 1998Advanced Technology Materials, Inc.Ferroelectric integrated circuit structure
US5725909 *9 Feb 199610 Mar 1998Catalina Coatings, Inc.Acrylate composite barrier coating process
US5749911 *24 Ene 199712 May 1998Cardiac Pacemakers, Inc.Implantable tissue stimulator incorporating deposited multilayer capacitor
US5763033 *30 Ene 19969 Jun 1998Becton, Dickinson And CompanyBlood collection tube assembly
US5779804 *11 May 199514 Jul 1998Canon Kabushiki KaishaGas feeding device for controlled vaporization of an organanometallic compound used in deposition film formation
US5811183 *11 Ago 199522 Sep 1998Shaw; David G.Acrylate polymer release coated sheet materials and method of production thereof
US5876503 *27 Nov 19962 Mar 1999Advanced Technology Materials, Inc.Multiple vaporizer reagent supply system for chemical vapor deposition utilizing dissimilar precursor compositions
US5877895 *20 Mar 19952 Mar 1999Catalina Coatings, Inc.Multicolor interference coating
US5904958 *20 Mar 199818 May 1999Rexam Industries Corp.Coating a substrate, condensation and adjustment of apertures vacuum chamber;
US5912069 *19 Dic 199615 Jun 1999Sigma Laboratories Of ArizonaFor use in explosives, propellants and pyrotechnics, radiation cross-linked multifunctional acrylate polymer materials
US5923970 *20 Nov 199713 Jul 1999Advanced Technology Materials, Inc.Method of fabricating a ferrolelectric capacitor with a graded barrier layer structure
US5935154 *8 Dic 199710 Ago 1999Cardiac Pacemakers, Inc.Implantable tissue stimulator incorporating deposited multilayer capacitor
US5945174 *1 Jul 199831 Ago 1999Delta V Technologies, Inc.Acrylate polymer release coated sheet materials and method of production thereof
US5968620 *22 Oct 199719 Oct 1999Becton Dickinson And CompanyBlood collection tube assembly
US5998236 *17 Feb 19987 Dic 1999Advanced Technology Materials, Inc.Process for controlled orientation of ferroelectric layers
US6008143 *2 Sep 199728 Dic 1999Hyundai Electronics Industries Co., Ltd.Metal organic chemical vapor deposition apparatus and deposition method
US6010751 *15 Dic 19974 Ene 2000Delta V Technologies, Inc.Polymerizing an acrylate monomer
US6012647 *1 Dic 199711 Ene 20003M Innovative Properties CompanyApparatus and method of atomizing and vaporizing
US6013337 *25 Mar 199711 Ene 2000Becton Dickinson And CompanyBlood collection tube assembly
US6040017 *2 Oct 199821 Mar 2000Sigma Laboratories, Inc.Forming a multilayer film polymer composites and evaporation, condensation, flash evaporation of mixtures, condensation and radiation curing
US6045864 *1 Dic 19974 Abr 20003M Innovative Properties CompanyVapor coating method
US6071688 *29 Jul 19986 Jun 2000Eastman Kodak CompanyContacting coating material on a support with uniform cloud of additive vaporized by flowing carrier gas through liquid phase additive
US6072689 *23 Feb 19996 Jun 2000Advanced Technology Materials, Inc.Ferroelectric capacitor and integrated circuit device comprising same
US6083628 *4 Abr 19964 Jul 2000Sigma Laboratories Of Arizona, Inc.Vacuum deposited, radiation polymerized acrylate monomer film; metallized packaging; heat, wear, and corrosion resistance
US6105501 *10 Jun 199822 Ago 2000Flex Products, Inc.High resolution lithographic printing plate suitable for imaging with laser-discharge article and method
US6143370 *26 Ago 19987 Nov 2000Northeastern UniversityMore flexible and stronger, medical stents,
US6146225 *30 Jul 199814 Nov 2000Agilent Technologies, Inc.Transparent, flexible permeability barrier for organic electroluminescent devices
US6146462 *7 May 199914 Nov 2000Astenjohnson, Inc.Structures and components thereof having a desired surface characteristic together with methods and apparatuses for producing the same
US617281026 Feb 19999 Ene 20013M Innovative Properties CompanyRetroreflective articles having polymer multilayer reflective coatings
US618432418 Dic 19976 Feb 2001Medtronic, Inc.Containing acrylic polymers as dielectric material
US620389829 Ago 199720 Mar 20013M Innovatave Properties CompanyArticle comprising a substrate having a silicone coating
US6207238 *16 Dic 199827 Mar 2001Battelle Memorial InstituteFlash evaporating a crosslinkable monomer into a polymer with the selected index of refraction, forming an evaporate, passing it to a glow discharge electrode creating a monomer plasma, cryocondensing plasma on a substrate and
US6207239 *16 Dic 199827 Mar 2001Battelle Memorial InstitutePlasma enhanced chemical deposition of conjugated polymer
US620734918 Mar 199927 Mar 2001Presstek, Inc.Depositing, onto a substrate, a mixture of a polymer precursor and a filler material comprising an inorganic compound; repeating a plurality of times with an increasing amount of filler relative to the polymer precursor; curing
US621048513 Jul 19993 Abr 2001Applied Materials, Inc.Chemical vapor deposition vaporizer
US621800411 Ago 199517 Abr 2001David G. ShawAcrylate polymer coated sheet materials and method of production thereof
US622421910 Abr 20001 May 20013M Innovative Properties CompanyMethod for making retroreflective articles having polymer multilayer reflective coatings
US6224948 *29 Sep 19971 May 2001Battelle Memorial InstitutePlasma enhanced chemical deposition with low vapor pressure compounds
US622843416 Dic 19988 May 2001Battelle Memorial InstitutePlasma polymerized polymer films, enhanced chemical vapordeposition with a flash evaporated feed source of a low vapor pressure compound.
US622843616 Dic 19988 May 2001Battelle Memorial InstitutePlasma polymerized polymer films, enhanced chemical vapordeposition with a flash evaporated feed source of a low vapor pressure compound.
US623193930 Ago 199615 May 2001Presstek, Inc.Acrylate composite barrier coating
US624320126 Jul 20005 Jun 20013M Innovative Properties CompanyRetroreflective articles having polymer multilayer reflective coatings
US624515020 Sep 199912 Jun 20013M Innovative Properties CompanyVapor coating apparatus
US6251334 *17 Mar 199926 Jun 2001Presstek, Inc.Composite constructions having mixed organic/inorganic layers
US6264747 *4 Ago 199924 Jul 20013M Innovative Properties CompanyApparatus for forming multicolor interference coating
US626869516 Dic 199831 Jul 2001Battelle Memorial InstituteUsed in displays; flexibility
US627420416 Dic 199814 Ago 2001Battelle Memorial InstituteMethod of making non-linear optical polymer
US630950815 Ene 199830 Oct 20013M Innovative Properties CompanySpinning disk evaporator
US634823712 Ene 200119 Feb 20023M Innovative Properties CompanyJet plasma process for deposition of coatings
US635003410 Abr 200026 Feb 20023M Innovative Properties CompanyRetroreflective articles having polymer multilayer reflective coatings
US635857031 Mar 199919 Mar 2002Battelle Memorial InstitutePlacing moving substrate into a vacuum chamber, degassing first liquid material selected from oligomer, resin, oligomer and monomer, resin and monomer to form a degassed first liquid material, depositing thin layer of liquid; curing
US639899922 Oct 19994 Jun 2002Avery Dennison CorporationProcess for making high aspect ratio reflective metal flakes
US641364520 Abr 20002 Jul 2002Battelle Memorial InstituteUltrabarrier substrates
US642000320 Dic 200016 Jul 20023M Innovative Properties CompanySheet including thermoplastic substrate, vapor deposited crosslinked acrylate layer, gas barrier material and second vapor deposited acrylate which was crosslinked before the gas barrier contacted any solid surface; low oxygen permeability
US645194718 Jul 200017 Sep 2002Medtronic, Inc.For use in medical devices such as pacemakers
US6468595 *13 Feb 200122 Oct 2002Sigma Technologies International, Inc.Vaccum deposition of cationic polymer systems
US647557127 Oct 19995 Nov 2002Matsushita Electric Industrial Co., Ltd.Magnetic recording medium such as a magnetic tape, a wrapping material, and an electronic component.
US649202620 Abr 200010 Dic 2002Battelle Memorial InstitutePolymer substrate having a high glass transition temperature (tg); and adjacent the substrate, a barrier stack of a barrier layer and polymer layer; for visual display devices; chemical resistance, wear resistance
US64975982 May 200124 Dic 2002Battelle Memorial InstituteEnvironmental barrier material for organic light emitting device and method of making
US649792419 Mar 200124 Dic 2002Battelle Memorial InstituteMethod of making non-linear optical polymer
US650356426 Feb 19997 Ene 20033M Innovative Properties CompanyMethod of coating microstructured substrates with polymeric layer(s), allowing preservation of surface feature profile
US650646131 Mar 199914 Ene 2003Battelle Memorial InstituteVacuum coating a thin layer of solvent-free monomer; curing
US6509065 *11 May 200121 Ene 2003Battelle Memorial InstitutePlasma enhanced chemical deposition of conjugated polymer
US652132430 Nov 199918 Feb 20033M Innovative Properties CompanyThermal transfer of microstructured layers
US652206725 Oct 199918 Feb 2003Battelle Memorial InstituteEncapsulated; stack contains acrylate polymer
US6544600 *19 Mar 20018 Abr 2003Battelle Memorial InstituteFlash evaporating a conjugated material and passing the evaporate to a glow discharge electrode creating a glow discharge plasma; then condensing on a substrate; crosslinking; kinetics
US654811218 Nov 199915 Abr 2003Tokyo Electron LimitedLiquid precursor such as copper or other metal-organic precursor is atomized at entry of high flow-conductance vaporizer, preferably with assistance of inert sweep gas
US654891215 May 200015 Abr 2003Battelle Memorial InstituteSemicoductor passivation using barrier coatings
US657032522 Jun 200127 May 2003Battelle Memorial InstituteEnvironmental barrier material for organic light emitting device and method of making
US657365220 Abr 20003 Jun 2003Battelle Memorial InstituteThe device includes a substrate, an environmentally sensitive display device adjacent to the substrate, and at least one first barrier stack adjacent to the environmentally sensitive display device. The barrier stack encapsulates the
US659413421 Feb 200115 Jul 2003Sigma Laboratories Of Arizona, Inc.Multilayer
US659711127 Nov 200122 Jul 2003Universal Display CorporationProtected organic optoelectronic devices
US661339516 Abr 20012 Sep 2003Battelle Memorial InstituteMixing liquid polymer precursor with molecular dopant; flash evaporating mixture forming a composite vapor; cryocondensing on a cool substrate forming a layer and crosslinking forming a layer of the composite polymer layer
US662386116 Abr 200123 Sep 2003Battelle Memorial InstituteMultilayer plastic substrates
US6627267 *11 May 200130 Sep 2003Battelle Memorial InstituteFlash evaportaion; glow discharges
US6656537 *19 Mar 20012 Dic 2003Battelle Memorial InstitutePlasma enhanced chemical deposition with low vapor pressure compounds
US670641221 Feb 200116 Mar 2004Sigma Laboratories Of ArizonaBarrier film for limiting transmission of oxygen and moisture therethrough
US670644918 Dic 200116 Mar 2004Moltech CorporationPolymer substrate and protective overcoatings
US673392421 Nov 200011 May 2004Moltech CorporationLithium anodes for electrochemical cells
US676535120 Dic 200120 Jul 2004The Trustees Of Princeton UniversityOrganic optoelectronic device structures
US677033731 Ene 20033 Ago 20043M Innovative Properties CompanyThermal transfer element is configured and arranged for transfer of at least a portion of microstructured layer to receptor while preserving microstructured features of that portion
US679742821 Nov 200028 Sep 2004Moltech CorporationLithium anodes for electrochemical cells
US680231521 Mar 200112 Oct 2004Hollingsorth & Vose CompanyVapor deposition treated electret filter media
US681182919 Mar 20012 Nov 2004Battelle Memorial InstituteCombination of flash evaporation with plasma enhanced chemical vapor deposition
US681504310 Oct 20029 Nov 20043M Innovative Properties CompanyMicrostructured substrates with profile-preserving polymeric coatings
US681829117 Ago 200216 Nov 20043M Innovative Properties CompanyDurable transparent EMI shielding film
US683595012 Abr 200228 Dic 2004Universal Display CorporationOrganic electronic devices with pressure sensitive adhesive layer
US683818321 Feb 20014 Ene 2005Sigma Laboratories Of Arizona, Inc.Optical filters
US685825919 Mar 200122 Feb 2005Battelle Memorial InstituteFlash evaporating the polymer precursor, discharging the evaporate to form plasma by a glow discharge electrode, cryocondensing plasma polymerization, crosslinking
US68638514 May 20018 Mar 2005Avery Dennison CorporationProcess for making angstrom scale and high aspect functional platelets
US686690128 Sep 200115 Mar 2005Vitex Systems, Inc.Method for edge sealing barrier films
US68873466 Sep 20013 May 20053M Innovative Properties CompanySpinning disk evaporator
US68883056 Nov 20013 May 2005Universal Display CorporationOrganic light emitting devices
US68974744 Abr 200324 May 2005Universal Display CorporationProtected organic electronic devices and methods for making the same
US690923025 Jun 200321 Jun 2005Battelle Memorial InstituteMethod of making molecularly doped composite polymer material
US692370213 Dic 20022 Ago 2005Battelle Memorial InstituteMethod of making encapsulated display devices
US692986417 Ago 200216 Ago 20053M Innovative Properties CompanyExtensible, visible light-transmissive and infrared-reflective film and methods of making and using the film
US693305117 Ago 200223 Ago 20053M Innovative Properties CompanyFlexible electrically conductive film
US69363816 Ago 200430 Ago 2005Moltech CorporationLithium anodes for electrochemical cells
US6942903 *4 Mar 200313 Sep 2005Matsushita Electric Industrial Co., Ltd.Steps of: supplying a deposition material in the form of a liquid onto a heated surface; heating and vaporizing the deposition material on the heated surface while the deposition material is undergoing movement;depositing the deposition
US696267122 May 20038 Nov 2005Battelle Memorial InstituteMultilayer plastic substrates
US699493316 Sep 20027 Feb 2006Oak Ridge Micro-Energy, Inc.Long life thin film battery and method therefor
US699864825 Ago 200314 Feb 2006Universal Display CorporationProtected organic electronic device structures incorporating pressure sensitive adhesive and desiccant
US70022948 Jun 200421 Feb 2006Universal Display CorporationMethod of protecting organic optoelectronic devices
US701236310 Ene 200214 Mar 2006Universal Display CorporationOLEDs having increased external electroluminescence quantum efficiencies
US70187132 Abr 200328 Mar 20063M Innovative Properties CompanyFlexible high-temperature ultrabarrier
US705277214 Ago 200330 May 20063M Innovative Properties Companya puncture resistant film of polyethylene and a polyester, a metal-free, light transmissible, static dissipative layer of two pairs of acrylate polymers, and a transparent conductive oxide layer; antistatic agent; low permeability of moisture vapor
US70779351 May 200218 Jul 2006General AtomicsO2 and H2O barrier material
US714074128 Dic 200428 Nov 20063M Innovative Properties CompanyColor shifting retroreflector and method of making same
US718646524 Ago 20016 Mar 20073M Innovative Properties CompanyTransparent conductive oxides for plastic flat panel displays
US7189436 *2 Ago 200413 Mar 20073M Innovative Properties CompanyFlash evaporation-plasma coating deposition method
US719536028 Dic 200427 Mar 20073M Innovative Properties CompanyPrismatic retroreflective article and method
US719883222 Abr 20053 Abr 2007Vitex Systems, Inc.Method for edge sealing barrier films
US721547317 Ago 20028 May 20073M Innovative Properties CompanyEnhanced heat mirror films
US724740823 May 200124 Jul 2007Sion Power CorporationLithium anodes for electrochemical cells
US726195015 Ago 200328 Ago 20073M Innovative Properties CompanyHaving a flexible support, an extensible metal or metal alloy layer, and a crosslinked polymeric protective layer and having at least one permanently deformed curved region; electromagnetic interference shielding films with reduced susceptibility to fracture or corrosion
US727629112 Dic 20022 Oct 20073M Innovative Properties CompanyLightweight, flexible, plastic substrate used to construct displays, including flat panel displays, to package materials and for electro luminescence lamps is coated with at least one layer, such that the substrate has desired barrier and
US728830924 Sep 200430 Oct 20073M Innovative Properties CompanyVapor depositing tripropylene glycol diacrylate, condensing and vapor phase polymerization, curing by beam radiation; producing polymeric protective coatings
US7300538 *16 Feb 200527 Nov 20073M Innovative Properties CompanySpinning disk evaporator
US731728024 Nov 20038 Ene 2008Tsinghua UniversityOrganic light-emitting devices and their encapsulation method and application of this method
US734757128 Dic 200525 Mar 20083M Innovative Properties CompanyPrismatic retroreflective article with fluorine- or silicon-containing prisms
US735147915 Ago 20031 Abr 20083M Innovative Properties CompanyDurable EMI shielding film
US739355712 Abr 20051 Jul 20083M Innovative Propertiesconnected visible light-transmissive metals or alloy layers separated by a visible light-transmissive crosslinked polymeric layer; electromagnetic interference shields; windshields
US748601914 Nov 20053 Feb 20093M Innovative Properties CompanyFlexible high-temperature ultrabarrier
US751091323 May 200631 Mar 2009Vitex Systems, Inc.Method of making an encapsulated plasma sensitive device
US7592043 *14 Feb 200522 Sep 2009Battelle Memorial InstituteMethod and apparatus for coating a patterned thin film on a substrate from a fluid source with continuous feed capability
US76117525 Oct 20073 Nov 20093M Innovative Properties CompanyMethod of making a microstructured coated article
US764892512 Jul 200719 Ene 2010Vitex Systems, Inc.Multilayer barrier stacks and methods of making multilayer barrier stacks
US772760129 Mar 20071 Jun 2010Vitex Systems, Inc.edge-sealed barrier stack includes a decoupling layer and at least two barrier layers(selected from metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxyborides); edges sealed against lateral moisture and gas diffusion
US776749824 Ago 20063 Ago 2010Vitex Systems, Inc.Encapsulated devices and method of making
US77718706 Abr 200610 Ago 2010Sion Power CorporationElectrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries
US77857309 Jul 200931 Ago 2010Sion Power CorporationElectrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries
US780590725 Oct 20075 Oct 2010E.I. Du Pont De Nemours And CompanyBreathable low-emissivity metalized sheets
US782008816 Ene 200426 Oct 2010Avery Dennison CorporationApplying multilayer laminate of vapor deposited metal and release agents to rotating cooled drum
US793178726 Feb 200326 Abr 2011Donald Bennett HilliardEnergetic vapor deposition means are addressed through the introduction of a novel means of vapor deposition, namely, an Electron-Assisted Deposition (EAD) process and apparatus. The EAD mode of film growth disclosed is generally achieved by
US794000413 Nov 200910 May 20113M Innovative Properties CompanyFlexible high-temperature ultrabarrier
US798091030 Ene 200919 Jul 20113M Innovative Properties CompanyFlexible high-temperature ultrabarrier
US803445210 Feb 201111 Oct 20113M Innovative Properties CompanyMoisture barrier coatings
US80760241 Jul 201013 Dic 2011Sion Power CorporationElectrode protection in both aqueous and non-aqueous electromechanical cells, including rechargeable lithium batteries
US808410223 Mar 200727 Dic 2011Sion Power CorporationSupplying vapors under reduced pressure with monomer; separate vapor streams; forming homogeneous film on substrate surface
US810571731 Oct 200731 Ene 2012Sion Power CorporationLithium anodes for electrochemical cells
US81979714 Mar 200812 Jun 2012Sion Power CorporationLithium anodes for electrochemical cells
US822704028 Dic 200724 Jul 20123M Innovative Properties CompanyMethod of curing metal alkoxide-containing films
US823642412 Ene 20097 Ago 2012General Electric CompanyMultilayer coating package on flexible substrates for electro-optical devices
US824175210 Dic 201014 Ago 20123M Innovative Properties CompanyTransparent conductive articles and methods of making same
US82992864 Dic 200730 Oct 2012Advanced Technology Materials, Inc.Source reagent compositions and method for forming metal films on a substrate by chemical vapor deposition
US832380118 Ene 20064 Dic 2012E I Du Pont De Nemours And CompanyProcess for forming a durable low emissivity moisture vapor permeable metallized sheet including a protective metal oxide layer
US83380344 Nov 201125 Dic 2012Sion Power CorporationElectrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries
US83504515 Jun 20088 Ene 20133M Innovative Properties CompanyUltrathin transparent EMI shielding film comprising a polymer basecoat and crosslinked polymer transparent dielectric layer
US841505413 Jun 20069 Abr 2013Sion Power CorporationLithium anodes for electrochemical cells
US84174745 Feb 20079 Abr 2013The Procter & Gamble CompanyMethods of use of substrate having properties of keratinous tissue
US843120925 Oct 200730 Abr 2013E I Du Pont De Nemours And CompanyBreathable low-emissivity metalized sheets
US8460762 *16 Dic 200911 Jun 2013Ideon LlcElectron beam curable composition for curing in a vacuum chamber
US848080415 Abr 20109 Jul 2013Panasonic CorporationThin film, method and apparatus for forming the same, and electronic component incorporating the same
US849701025 Oct 200730 Jul 2013E I Du Pont De Nemours And CompanyBreathable low-emissivity metalized sheets
US853484915 Abr 201017 Sep 20133M Innovative Properties CompanyRetroreflecting optical construction
US854194225 Jun 201224 Sep 20133M Innovative Properties CompanyTransparent conductive articles and methods of making same
US859033831 Dic 200926 Nov 2013Samsung Mobile Display Co., Ltd.Evaporator with internal restriction
US860368015 Nov 201210 Dic 2013Sion Power CorporationElectrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries
US86177484 Dic 200731 Dic 2013Sion Power CorporationSeparation of electrolytes
US862355710 May 20127 Ene 2014Sion Power CorporationLithium anodes for electrochemical cells
US862885923 Abr 201214 Ene 20143M Innovative Properties CompanyBarrier film
US863004021 Oct 200814 Ene 20143M Innovative Properties CompanyMulti-component films for optical display filters
US8658248 *28 Dic 200625 Feb 20143M Innovative Properties CompanyMethod for atomizing material for coating processes
US872866122 Oct 201320 May 2014Sion Power CorporationLithium anodes for electrochemical cells
US875377123 Jul 200717 Jun 2014Sion Power CorporationLithium anodes for electrochemical cells
US880845711 Abr 200319 Ago 2014Samsung Display Co., Ltd.Apparatus for depositing a multilayer coating on discrete sheets
US880881126 Mar 201019 Ago 20143M Innovative Properties CompanyProcess and apparatus for a nanovoided article
US20110143046 *16 Dic 200916 Jun 2011Mikhail LaksinElectron beam curable composition for curing in a vacuum chamber
USRE40531 *12 Jul 20047 Oct 2008Battelle Memorial InstituteUltrabarrier substrates
USRE4078712 Jul 200423 Jun 2009Battelle Memorial InstituteMultilayer plastic substrates
EP0787821A224 Ene 19976 Ago 1997Becton Dickinson and CompanyBlood collection tube assembly
EP0787823A224 Ene 19976 Ago 1997Becton Dickinson and CompanyBlood collection tube assembly
EP0787825A124 Ene 19976 Ago 1997Becton Dickinson and CompanyBlood collection tube assembly
EP0787826A124 Ene 19976 Ago 1997Becton Dickinson and CompanyBlood collection tube assembly
EP1019562A1 *29 Sep 199819 Jul 2000Battelle Memorial InstitutePlasma enhanced chemical deposition with low vapor pressure compounds
EP1134063A1 *27 Oct 199919 Sep 2001Matsushita Electric Industrial Co., Ltd.Method of producing thin resin films
EP1228272A123 Ago 20007 Ago 2002THE PROCTER & GAMBLE COMPANYDurably wettable liquid pervious webs prepared using a radiation curing process
EP1366927A124 Mar 20003 Dic 20033M Innovative Properties CompanyThermal transfer of microstructured layers
EP1958981A214 Feb 200820 Ago 2008FUJIFILM CorporationBarriere laminate, barrier film substrate, methods for producing them, and device
EP2042545A225 Jul 20081 Abr 2009Fujifilm CorporationBarrier film substrate and method for producing same, and organic device
EP2045355A118 Sep 20088 Abr 2009Fujifilm CorporationGas-barrier film and organic device comprising same
EP2055734A211 Jun 20086 May 2009FUJIFILM CorporationGas barrier film and organic device using the same
EP2085496A130 Ene 20095 Ago 2009FUJIFILM CorporationMethod for producing functional film
EP2085497A130 Ene 20095 Ago 2009FUJIFILM CorporationMethod for producing functional film
EP2103646A120 Mar 200923 Sep 2009Fujifilm CorporationBarrier laminate and method for producing same, barrier film substrate, device and optical component
EP2113310A1 *29 Abr 20094 Nov 2009FUJIFILM CorporationFilm depositing apparatus
EP2199427A215 Dic 200923 Jun 2010Fujifilm CorporationMethod for producing laminate
EP2277698A131 Mar 200426 Ene 20113M Innovative Properties CompanyFlexible high-temperature ultrabarrier
EP2280297A115 Ago 20032 Feb 20113M Innovative Properties Co.Enhanced heat mirror films
EP2426164A131 Ago 20117 Mar 2012Fujifilm CorporationFunctional film and method of manufacturing functional film
WO1993012266A1 *11 Dic 199224 Jun 1993Advanced Tech MaterialsApparatus and method for delivery of involatile reagents
WO1995010117A1 *4 Oct 199413 Abr 1995Catalina Coatings IncCross-linked acrylate coating material useful for forming capacitor dielectrics and oxygen barriers
WO2001036707A1 *15 Sep 200025 May 2001Tokyo Electron Arizona IncApparatus and method for delivery of precursor vapor from low vapor pressure liquid sources to a cvd chamber
WO2001039302A121 Nov 200031 May 2001Moltech CorpLithium anodes for electrochemical cells
WO2002064268A1 *7 Feb 200222 Ago 2002Sigma Technologies InternationVacuum deposition of cationic polymer systems
WO2003063223A1 *19 Dic 200231 Jul 2003Ball Semiconductor IncMethod for making a gas permeable enclosure for micromachine devices
WO2005120136A2 *25 May 200515 Dic 2005Michael G MikhaelLarge-area electroluminescent light-emitting devices
WO2009002892A122 Jun 200831 Dic 2008Univ ColoradoProtective coatings for organic electronic devices made using atomic layer deposition and molecular layer deposition techniques
WO2011062836A111 Nov 201026 May 20113M Innovative Properties CompanyMulti-layer optical films
WO2012047422A131 Ago 201112 Abr 20123M Innovative Properties CompanyAnti-reflective articles with nanosilica-based coatings
WO2012047749A130 Sep 201112 Abr 20123M Innovative Properties CompanyAnti-reflective articles with nanosilica-based coatings and barrier layer
WO2012174393A115 Jun 201220 Dic 2012Sion Power CorporationPlating technique for electrode
WO2014068036A131 Oct 20138 May 2014Basf SePolymers for use as protective layers and other components in electrochemical cells
WO2014081917A221 Nov 201330 May 20143M Innovative Properties CompanyMultilayer film including first and second dielectric layers
WO2014081918A221 Nov 201330 May 20143M Innovative Properties CompanyMultilayer film including first and second dielectric layers
Clasificaciones
Clasificación de EE.UU.427/497, 427/509, 392/399, 427/81, 427/248.1, 427/255.6, 427/80, 427/127, 427/600
Clasificación internacionalB05D7/24, B01D3/06, H01G4/14, B01D1/16, C23C16/448
Clasificación cooperativaH01G4/145, B05D1/60, B01D3/06, B01D1/16, C23C16/4486
Clasificación europeaB05D1/60, B01D3/06, C23C16/448H, B01D1/16, H01G4/14B
Eventos legales
FechaCódigoEventoDescripción
1 Jun 2011ASAssignment
Owner name: SPECTRUM CONTROL, INC., PENNSYLVANIA
Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:PNC BANK, NATIONAL ASSOCIATION, AS AGENT;REEL/FRAME:026373/0632
Effective date: 20110601
10 Sep 2006ASAssignment
Owner name: SIGMA LABORATORIES OF ARIZONA, LLC, ARIZONA
Free format text: LICENSE;ASSIGNOR:SIGMA LABORATORIES OF ARIZONA, INC.;REEL/FRAME:018239/0852
Effective date: 20060717
16 Ene 2006ASAssignment
Owner name: PNC BANK, NATIONAL ASSOCIATION, PENNSYLVANIA
Free format text: SECURITY AGREEMENT;ASSIGNOR:SPECTRUM CONTROL, INC.;REEL/FRAME:017198/0210
Effective date: 20051209
1 Mar 2002ASAssignment
Owner name: 3M INNOVATIVE PROPERTIES COMPANY, MINNESOTA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DELTA V TECHNOLOGIES, INC.;PRESSTEK, INC.;REEL/FRAME:012653/0404
Effective date: 20011009
Owner name: 3M INNOVATIVE PROPERTIES COMPANY P.O. BOX 33427 ST
Owner name: 3M INNOVATIVE PROPERTIES COMPANY P.O. BOX 33427ST.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DELTA V TECHNOLOGIES, INC. /AR;REEL/FRAME:012653/0404
7 Feb 2002FPAYFee payment
Year of fee payment: 12
27 Mar 2000ASAssignment
Owner name: PNC BANK, NATIONAL ASSOCIATION, AS AGENT, PENNSYLV
Free format text: AMENDMENT TO SECURITY AGREEMENT RECORDED 3/29/99 ON REEL 9857 FRAME 0647.;ASSIGNOR:SPECTRUM CONTROL, INC.;REEL/FRAME:010703/0756
Effective date: 20000327
Owner name: PNC BANK, NATIONAL ASSOCIATION, AS AGENT NINTH AND
29 Mar 1999ASAssignment
Owner name: PNC BANK, NATIONAL ASSOCIATION, AS AGENT, PENNSYLV
Free format text: SECURITY AGREEMENT;ASSIGNOR:SPECTRUM CONTROL, INC.;REEL/FRAME:009857/0647
Effective date: 19990326
20 Feb 1998FPAYFee payment
Year of fee payment: 8
4 Ago 1997ASAssignment
Owner name: CATALINA COATINGS, INC., A CORP. OF ARIZONA, ARIZO
Free format text: EXCLUSIVE LICENSE AGEEMENT;ASSIGNOR:SPECTRUM CONTROL, INC., A CORP. OF DELAWARE;REEL/FRAME:008628/0001
Effective date: 19931208
25 Feb 1994FPAYFee payment
Year of fee payment: 4
21 Jul 1992CCCertificate of correction